5: AZO POLYMER COLLOIDAL SPHERES in Java

Writer qr bidimensional barcode in Java 5: AZO POLYMER COLLOIDAL SPHERES
CHAPTER 5: AZO POLYMER COLLOIDAL SPHERES
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the BP-AZ-CA chains start to aggregate. As the water content further increases, the less hydrophobic BP-AZ-CA chains assemble on the PEAPE-dominated cores, which nally results in the formation of the hybrid colloids. The nonuniform distribution of the two components and its in uence on the photoresponsive properties are further discussed in the following section.
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5.4. PHOTORESPONSIVE PROPERTIES OF AZO POLYMER COLLOIDAL SPHERES
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Depending on the composition and preparation conditions, the azo polymer colloidal spheres can exhibit different photoresponsive properties triggered by the photoisomerization of the azo chromophores. The photoinduced variations are related to both the isomerization features of the azo chromophores and the structures of the colloidal matrices. For colloids containing azobenzene-type chromophores, the photochromic variation caused by isomerization can be measured by UV-vis spectroscopy. As mentioned earlier, the isomerization rate and degree have been used as a tool to monitor the structure variation. Compared with the isolated chains and loose aggregates, the photoinduced isomerization rate and degree are much lower for the colloids in their nal collapsed state, which is due to the compact inner structure after the collapse. For the colloids containing relatively small amount of pseudostilbene-type azo chromophores, the shape of the colloids remains unaltered after the linearly polarized Ar+ laser light irradiation, but the azo chromophores in colloids can be driven by the linearly polarized light to align perpendicularly to the polarization direction. This property is discussed in Section 5.5 together with those observed for the 2-D colloidal arrays. Most signi cant photoresponsive variation is the shape deformation induced by Ar+ laser irradiation, which can be observed for the colloids containing pseudostilbene-type chromophores. This photoresponsive property is discussed in this section in detail.
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5.4.1. Deformation Induced by Interfering Ar+ Laser Beams
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The colloidal spheres formed from the polymers containing pseudostilbene-type chromophores, such as BP-AZ-CA, can be signi cantly elongated upon irradiation of interfering Ar+ laser beams (Li et al., 2005b). In a typical case, an Ar+ laser beam at 488 nm with intensity of B150 mW/cm2 was used as the light source. The colloidal spheres on substrates were prepared by methods such as casting the water suspension of the colloidal spheres on a silicon wafer or copper grid and then drying in a vacuum oven at 301C for 12 h. The light irradiation experiments were carried out at room temperature under an ambient condition. When the colloidal spheres are exposed to the interference pattern of the p-polarized Ar+ laser beams, signi cant shape deformation can be induced. The shape deformation can be observed by SEM, atomic force microscopy (AFM), and TEM. Figure 5.10 shows typical TEM and SEM images of the colloidal spheres after the laser
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5.4. PHOTORESPONSIVE PROPERTIES OF AZO POLYMER COLLOIDAL SPHERES
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Figure 5.10. (a) TEM image of the spherical colloids before the irradiation. (b) TEM and (c) SEM images of the deformed colloids obtained from the azo polymer colloidal spheres after they are exposed to interfering polarized Ar+ laser beams for 10 min.The averaged size of the spheres is 295 nm, and the scale bar in the TEM picture is 300 nm. Source: From Li et al., 2005b.
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irradiation for 10 min, and TEM image of the colloids before light irradiation is also given for comparison. It can be seen that after the irradiation, the spheres are deformed to ellipsoids, which can also be con rmed by AFM observations. The elongation occurs in the polarization direction of the laser beam, which is also the grating vector direction of the interference patterns. In the testing period (15 min), the colloids can be continuously elongated by the light irradiation. The average major-to-minor axis ratio (l/d) of the colloids can be used to indicate the deformation degree of the colloids. Figure 5.11 shows the SEM images of colloidal particles observed before the irradiation and after the irradiation for different time periods. After 5-min irradiation, obvious change in the shape can be observed. As the irradiation time increases, the elongation can be observed to increase continuously. The relationship between the average major-tominor ratio (estimated statistically from SEM images of 100 colloidal particles) and the irradiation time is given in Fig. 5.12. The major-to-minor ratio increases almost linearly with the irradiation time increase in the testing range. The colloidal sphere deformation could be attributed to the optically induced electric eld gradient, which has been used by Kumar et al. (1998) to explain the SRG formation. The polymers used to construct the photodeformable colloids can also show sensitive properties to form SRG. Photoinduced mass migration has been used to account for the SRG formation, where the polymer chains are driven by light to move from bright to dark regions. The colloid deformation could also be caused by the mass migration related to the electric eld gradient force.
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